High productivity combinatorial workflow for photoresist strip applications

ABSTRACT

Electrical testing of metal oxide semiconductor (MOS) high-k capacitor structures is used to evaluate photoresist strip or cleaning chemicals using a combinatorial workflow. The electrical testing can be able to identify the damages on the high-k dielectrics, permitting a selection of photoresist strip chemicals to optimize the process conditions in the fabrication of semiconductor devices. The high productivity combinatorial technique can provide a compatibility evaluation of photoresist strip chemicals with high-k devices.

FIELD OF THE INVENTION

The present invention relates generally to combinatorial methods fordevice process development. More specifically, combinatorial methods ofdeveloping fabrication processes for gate electrode and metal gateelectrode devices with regard to wet process chemicals, such asphotoresist strip chemicals.

BACKGROUND OF THE INVENTION

Advances in semiconductor processing have demanded ever-increasing highfunctional density with continuous size scaling. This scaling processhas led to the adoption high-k gate dielectrics and metal gateelectrodes in metal gate stacks in semiconductor devices.

High-k gate dielectrics can offer a way to scale down the thickness ofthe gate dielectric with acceptable gate leakage current. The use ofhigh-k gate dielectrics is often accompanied by a metal gate electrode,since thin gate dielectric layers may cause poly depletion, affectingthe device operation and performance. Metal gate electrodes further havean advantage of higher electrical conductance, as compared to polygates, and thus can improve signal propagation times.

The manufacture of high-k dielectric devices entails the integration andsequencing of many unit processing steps, with potential new processdevelopments, since in general, high-k gate dielectrics are much moresensitive to process conditions than silicon dioxide. For example,organic solvents are typically used in stripping photoresist which hasbeen used for patterning of high-k materials, to address the sensitivityof high-k dielectric materials to standard wet processes. However,organic solvents can leave residual carbon on the high-k gate stacks,affecting subsequent fabrication processes, and consequently theperformance of the high-k gate structures. As an example, unremovedresidual photoresist on high-k dielectrics has been observed to causethreshold voltage shift with increasing inversion thickness. The precisesequencing and integration of the unit processing steps enables theformation of functional devices meeting desired performance metrics suchas power efficiency, signal propagation, and reliability.

As part of the discovery, optimization and qualification of each unitprocess, it is desirable to be able to i) test different materials, ii)test different processing conditions within each unit process module,iii) test different sequencing and integration of processing moduleswithin an integrated processing tool, iv) test different sequencing ofprocessing tools in executing different process sequence integrationflows, and combinations thereof in the manufacture of devices such asintegrated circuits. In particular, there is a need to be able to testi) more than one material, ii) more than one processing condition, iii)more than one sequence of processing conditions, iv) more than oneprocess sequence integration flow, and combinations thereof,collectively known as “combinatorial process sequence integration”, on asingle monolithic substrate without the need of consuming the equivalentnumber of monolithic substrates per material(s), processingcondition(s), sequence(s) of processing conditions, sequence(s) ofprocesses, and combinations thereof. This can greatly improve both thespeed and reduce the costs associated with the discovery,implementation, optimization, and qualification of material(s),process(es), and process integration sequence(s) required formanufacturing.

Systems and methods for High Productivity Combinatorial (HPC) processingare described in U.S. Pat. No. 7,544,574 filed on Feb. 10, 2006, U.S.Pat. No. 7,824,935 filed on Jul. 2, 2008, U.S. Pat. No. 7,871,928 filedon May 4, 2009, U.S. Pat. No. 7,902,063 filed on Feb. 10, 2006, and U.S.Pat. No. 7,947,531 filed on Aug. 28, 2009 which are all hereinincorporated by reference. Systems and methods for HPC processing arefurther described in U.S. patent application Ser. No. 11/352,077 filedon Feb. 10, 2006, claiming priority from Oct. 15, 2005, U.S. patentapplication Ser. No. 11/419,174 filed on May 18, 2006, claiming priorityfrom Oct. 15, 2005, U.S. patent application Ser. No. 11/674,132 filed onFeb. 12, 2007, claiming priority from Oct. 15, 2005, and U.S. patentapplication Ser. No. 11/674,137 filed on Feb. 12, 2007, claimingpriority from Oct. 15, 2005 which are all herein incorporated byreference.

HPC processing techniques have been successfully adapted to wet chemicalprocessing such as etching and cleaning. HPC processing techniques havealso been successfully adapted to deposition processes such as physicalvapor deposition (PVD), atomic layer deposition (ALD), and chemicalvapor deposition (CVD). However, HPC processing techniques have not beensuccessfully adapted to the development of wet chemicals to preventdegradation of high-k device performance.

Therefore, there is a need to apply high productivity combinatorialtechniques to the development and investigation of liquid materials andwet processes for the manufacture of high-k devices.

SUMMARY OF THE DESCRIPTION

In some embodiments, the present invention discloses electrical testingof metal oxide semiconductor (MOS) capacitor structures to evaluate wetprocessing chemicals. Advanced devices can utilize novel dielectricmaterials, such as high-k gate dielectrics or low-k interleveldielectrics, which might experience performance side effects underexposure to wet processing chemicals, such as photoresist strip orcleaning chemicals. The present electrical testing can be able toidentify the damages on the dielectrics, permitting a selection of wetprocessing chemicals to optimize the process conditions for dielectriclayers in the fabrication of semiconductor devices

In some embodiments, the present invention discloses combinatorialworkflow for evaluating wet processing chemicals, such as photoresiststrip chemicals, to provide optimized process conditions for gate stackformation, preferably for metal gate stack using high-k dielectrics. MOScapacitor devices are combinatorially fabricated on multiple regions ofa substrate, with each region exposed to a different photoresist stripchemical. The MOS capacitor devices are then electrically tested, andthe electrical data are compared to categorize the potential damages ofdifferent photoresist strip chemicals and identify suitable photoresiststrip chemicals based on desired device requirements.

In some embodiments, the invention discloses combinatorially exposingonly the dielectric layer to photoresist strip chemicals beforeelectrically testing the MOS devices. In other embodiments, theinvention discloses combinatorially exposing both the dielectric layerand the electrode to photoresist strip chemicals before electricallytesting the MOS devices.

BRIEF DESCRIPTION OF THE DRAWINGS

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The drawings are not to scale and the relative dimensionsof various elements in the drawings are depicted schematically and notnecessarily to scale.

The techniques of the present invention can readily be understood byconsidering the following detailed description in conjunction with theaccompanying drawings, in which:

FIG. 1 illustrates a schematic diagram, 100, for implementingcombinatorial processing and evaluation using primary, secondary, andtertiary screening.

FIG. 2 is a simplified schematic diagram illustrating a generalmethodology for combinatorial process sequence integration that includessite isolated processing and/or conventional processing in accordancewith one embodiment of the invention.

FIG. 3 illustrates an exemplary flowchart for screening wet processchemicals, such as photoresist strip chemicals, according to someembodiments of the present invention.

FIGS. 4A-4E illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer tophotoresist strip chemical according to some embodiments of the presentinvention.

FIG. 5 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer according to someembodiments of the present invention.

FIGS. 6A-6E illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer and theelectrode to photoresist strip chemical according to some embodiments ofthe present invention.

FIG. 7 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer and the electrodelayer according to some embodiments of the present invention.

FIGS. 8A-8F illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer and theelectrode to photoresist strip chemical according to some embodiments ofthe present invention.

FIG. 9 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer and the electrodelayer according to some embodiments of the present invention.

FIGS. 10A-10B illustrate other exemplary test structures according tosome embodiments of the present invention.

FIG. 11 illustrates a schematic diagram of a combinatorial PVD systemaccording to an embodiment described herein.

FIG. 12 illustrates a schematic diagram of a substrate that has beenprocessed in a combinatorial manner.

FIG. 13 illustrates a schematic diagram of a combinatorial wetprocessing system according to an embodiment described herein.

FIG. 14 illustrates a flow diagram for forming simple test structuresaccording to an embodiment described herein.

FIG. 15 illustrates a flow diagram for forming another exemplary teststructure evaluation according to an embodiment described herein.

FIG. 16 illustrates a flow diagram for forming another exemplary teststructure evaluation according to an embodiment described herein.

FIG. 17 illustrates another flow diagram for forming an exemplary teststructure evaluation according to an embodiment described herein.

FIG. 18 illustrates a flatband voltage shift comparison between 8different photoresist strip chemicals according to some embodiments ofthe present invention.

DETAILED DESCRIPTION

A detailed description of one or more embodiments is provided belowalong with accompanying figures. The detailed description is provided inconnection with such embodiments, but is not limited to any particularexample. The scope is limited only by the claims and numerousalternatives, modifications, and equivalents are encompassed. Numerousspecific details are set forth in the following description in order toprovide a thorough understanding. These details are provided for thepurpose of example and the described techniques may be practicedaccording to the claims without some or all of these specific details.For the purpose of clarity, technical material that is known in thetechnical fields related to the embodiments has not been described indetail to avoid unnecessarily obscuring the description.

In FIGS. 3-9 below, exemplary methods for evaluating wet chemicals, suchas photoresist strip chemicals, are illustrated using a simple planarstructure. Those skilled in the art will appreciate that the descriptionand teachings to follow can be readily applied to any simple or complextesting methodology. The drawings are for illustrative purposes only anddo not limit the application of the present invention.

“Combinatorial Processing” generally refers to techniques ofdifferentially processing multiple regions of one or more substrates.Combinatorial processing can be used to produce and evaluate differentmaterials, chemicals, processes, process and integration sequences, andtechniques related to semiconductor fabrication. For example,combinatorial processing can be used to determine optimal processingparameters (e.g., power, time, reactant flow rates, temperature, etc.)of dry processing techniques such as dry etching (e.g., plasma etching,flux-based etching, reactive ion etching (RIE)) and dry depositiontechniques (e.g., physical vapor deposition (PVD), chemical vapordeposition (CVD), atomic layer deposition (ALD), etc.).

Combinatorial processing generally varies materials, unit processes orprocess sequences across multiple regions on a substrate. The variedmaterials, unit processes, or process sequences can be evaluated (e.g.,characterized) to determine whether further evaluation of certainprocess sequences is warranted or whether a particular solution issuitable for production or high volume manufacturing.

FIG. 1 illustrates a schematic diagram, 100, for implementingcombinatorial processing and evaluation using primary, secondary, andtertiary screening. The schematic diagram, 100, illustrates that therelative number of combinatorial processes run with a group ofsubstrates decreases as certain materials and/or processes are selected.Generally, combinatorial processing includes performing a large numberof processes during a primary screen, selecting promising candidatesfrom those processes, performing the selected processing during asecondary screen, selecting promising candidates from the secondaryscreen for a tertiary screen, and so on. In addition, feedback fromlater stages to earlier stages can be used to refine the successcriteria and provide better screening results.

For example, thousands of materials are evaluated during a materialsdiscovery stage, 102. Materials discovery stage, 102, is also known as aprimary screening stage performed using primary screening techniques.Primary screening techniques may include dividing substrates intocoupons and depositing materials using varied processes. The materialsare then evaluated, and promising candidates are advanced to thesecondary screen, or materials and process development stage, 104.Evaluation of the materials is performed using metrology tools such aselectronic testers and imaging tools (i.e., microscopes).

The materials and process development stage, 104, may evaluate hundredsof materials (i.e., a magnitude smaller than the primary stage) and mayfocus on the processes used to deposit or develop those materials.Promising materials and processes are again selected, and advanced tothe tertiary screen or process integration stage, 106, where tens ofmaterials and/or processes and combinations are evaluated. The tertiaryscreen or process integration stage, 106, may focus on integrating theselected processes and materials with other processes and materials.

The most promising materials and processes from the tertiary screen areadvanced to device qualification, 108. In device qualification, thematerials and processes selected are evaluated for high volumemanufacturing, which normally is conducted on full substrates withinproduction tools, but need not be conducted in such a manner. Theresults are evaluated to determine the efficacy of the selectedmaterials and processes. If successful, the use of the screenedmaterials and processes can proceed to pilot manufacturing, 110.

The schematic diagram, 100, is an example of various techniques that maybe used to evaluate and select materials and processes for thedevelopment of new materials and processes. The descriptions of primary,secondary, etc. screening and the various stages, 102-110, are arbitraryand the stages may overlap, occur out of sequence, be described and beperformed in many other ways.

This application benefits from High Productivity Combinatorial (HPC)techniques described in U.S. patent application Ser. No. 11/674,137filed on Feb. 12, 2007 which is hereby incorporated for reference in itsentirety. Portions of the '137 application have been reproduced below toenhance the understanding of the present invention. The embodimentsdescribed herein enable the application of combinatorial techniques toprocess sequence integration in order to arrive at a globally optimalsequence of high-k device fabrication process with metal gate byconsidering interaction effects between the unit manufacturingoperations, the process conditions used to effect such unitmanufacturing operations, hardware details used during the processing,as well as materials characteristics of components utilized within theunit manufacturing operations. Rather than only considering a series oflocal optimums, i.e., where the best conditions and materials for eachmanufacturing unit operation is considered in isolation, the embodimentsdescribed below consider interactions effects introduced due to themultitude of processing operations that are performed and the order inwhich such multitude of processing operations are performed whenfabricating a high-k device. A global optimum sequence order istherefore derived, and as part of this derivation, the unit processes,unit process parameters and materials used in the unit processoperations of the optimum sequence order are also considered.

The embodiments described further analyze a portion or sub-set of theoverall process sequence used to manufacture a semiconductor device.Once the subset of the process sequence is identified for analysis,combinatorial process sequence integration testing is performed tooptimize the materials, unit processes, hardware details, and processsequence used to build that portion of the device or structure. Duringthe processing of some embodiments described herein, structures areformed on the processed substrate which are equivalent to the structuresformed during actual production of the high-k device. For example, suchstructures may include, but would not be limited to, high-k dielectriclayers, metal gate layers, spacers, or any other series of layers orunit processes that create an intermediate structure found onsemiconductor devices. While the combinatorial processing varies certainmaterials, unit processes, hardware details, or process sequences, thecomposition or thickness of the layers or structures or the action ofthe unit process, such as cleaning, surface preparation, deposition,surface treatment, etc. is substantially uniform through each discreteregion. Furthermore, while different materials or unit processes may beused for corresponding layers or steps in the formation of a structurein different regions of the substrate during the combinatorialprocessing, the application of each layer or use of a given unit processis substantially consistent or uniform throughout the different regionsin which it is intentionally applied. Thus, the processing is uniformwithin a region (inter-region uniformity) and between regions(intra-region uniformity), as desired. It should be noted that theprocess can be varied between regions, for example, where a thickness ofa layer is varied or a material may be varied between the regions, etc.,as desired by the design of the experiment.

The result is a series of regions on the substrate that containstructures or unit process sequences that have been uniformly appliedwithin that region and, as applicable, across different regions. Thisprocess uniformity allows comparison of the properties within and acrossthe different regions such that the variations in test results are dueto the varied parameter (e.g., materials, unit processes, unit processparameters, hardware details, or process sequences) and not the lack ofprocess uniformity. In the embodiments described herein, the positionsof the discrete regions on the substrate can be defined as needed, butare preferably systematized for ease of tooling and design ofexperimentation. In addition, the number, variants and location ofstructures within each region are designed to enable valid statisticalanalysis of the test results within each region and across regions to beperformed.

FIG. 2 is a simplified schematic diagram illustrating a generalmethodology for combinatorial process sequence integration that includessite isolated processing and/or conventional processing in accordancewith one embodiment of the invention. In one embodiment, the substrateis initially processed using conventional process N. In one exemplaryembodiment, the substrate is then processed using site isolated processN+1. During site isolated processing, an HPC module may be used, such asthe HPC module described in U.S. patent application Ser. No. 11/352,077filed on Feb. 10, 2006. The substrate can then be processed using siteisolated process N+2, and thereafter processed using conventionalprocess N+3. Testing is performed and the results are evaluated. Thetesting can include physical, chemical, acoustic, magnetic, electrical,optical, etc. tests. From this evaluation, a particular process from thevarious site isolated processes (e.g. from steps N+1 and N+2) may beselected and fixed so that additional combinatorial process sequenceintegration may be performed using site isolated processing for eitherprocess N or N+3. For example, a next process sequence can includeprocessing the substrate using site isolated process N, conventionalprocessing for processes N+1, N+2, and N+3, with testing performedthereafter.

It should be appreciated that various other combinations of conventionaland combinatorial processes can be included in the processing sequencewith regard to FIG. 2. That is, the combinatorial process sequenceintegration can be applied to any desired segments and/or portions of anoverall process flow. Characterization, including physical, chemical,acoustic, magnetic, electrical, optical, etc. testing, can be performedafter each process operation, and/or series of process operations withinthe process flow as desired. The feedback provided by the testing isused to select certain materials, processes, process conditions, andprocess sequences and eliminate others. Furthermore, the above flows canbe applied to entire monolithic substrates, or portions of monolithicsubstrates such as coupons.

Under combinatorial processing operations the processing conditions atdifferent regions can be controlled independently. Consequently, processmaterial amounts, reactant species, processing temperatures, processingtimes, processing pressures, processing flow rates, processing powers,processing reagent compositions, the rates at which the reactions arequenched, deposition order of process materials, process sequence steps,hardware details, etc., can be varied from region to region on thesubstrate. Thus, for example, when exploring materials, a processingmaterial delivered to a first and second region can be the same ordifferent. If the processing material delivered to the first region isthe same as the processing material delivered to the second region, thisprocessing material can be offered to the first and second regions onthe substrate at different concentrations. In addition, the material canbe deposited under different processing parameters. Parameters which canbe varied include, but are not limited to, process material amounts,reactant species, processing temperatures, processing times, processingpressures, processing flow rates, processing powers, processing reagentcompositions, the rates at which the reactions are quenched, atmospheresin which the processes are conducted, an order in which materials aredeposited, hardware details of the gas distribution assembly, etc. Itshould be appreciated that these process parameters are exemplary andnot meant to be an exhaustive list as other process parameters commonlyused in semiconductor manufacturing may be varied.

As mentioned above, within a region, the process conditions aresubstantially uniform, in contrast to gradient processing techniqueswhich rely on the inherent non-uniformity of the material deposition.That is, the embodiments, described herein locally perform theprocessing in a conventional manner, e.g., substantially consistent andsubstantially uniform, while globally over the substrate, the materials,processes, and process sequences may vary. Thus, the testing will findoptimums without interference from process variation differences betweenprocesses that are meant to be the same. It should be appreciated that aregion may be adjacent to another region in one embodiment or theregions may be isolated and, therefore, non-overlapping. When theregions are adjacent, there may be a slight overlap wherein thematerials or precise process interactions are not known, however, aportion of the regions, normally at least 50% or more of the area, isuniform and all testing occurs within that region. Further, thepotential overlap is only allowed with material of processes that willnot adversely affect the result of the tests. Both types of regions arereferred to herein as regions or discrete regions.

In some embodiments, the present invention discloses electrical testingof semiconductor devices to evaluate wet processing chemicals, forexample, to identify chemicals or process conditions that can affect thedevice performance. The wet processing chemicals can be cleaningchemicals, wet etch chemicals, or photoresist strip chemicals. In thefollowing description, photoresist strip chemicals are described inpreferred embodiments, but the invention is not so limited, and can beused for evaluating any wet processing chemical.

Advanced semiconductor devices can employ novel materials such as metalgate electrodes and high-k dielectrics, which comprise dielectricmaterials having a dielectric constant greater than that of silicondioxide. Typically high-k dielectric materials include aluminum oxide,hafnium oxide, zirconium oxide, tantalum oxide, titanium oxide, or theiralloys such as hafnium silicon oxide or zirconium silicon oxide. Metalgate materials typically comprise a refractive metal or a nitride of arefractive metal, such as titanium nitride, titanium aluminum nitride,or titanium lanthanum nitride. High-k dielectric and metal electrodematerials can be highly sensitive to wet processing chemicals, and canexhibit device degradation if improper chemicals or process conditionsare used.

In some embodiments, the present invention discloses methods to evaluatepotential impact of various chemistries and processes on transistorperformance and reliability, comprising electrical testing of metaloxide semiconductor (MOS) capacitor structures. MOS capacitor structurescan be quickly and economically fabricated, permitting evaluatingpotential device degradations of various chemicals and processconditions with fast turn-around times. Electrical testing can providedevice damage information with adequate sensitivity to permitdistinguishing the effects of various wet chemical materials and devicefabrication processes. For example, flatband voltage measurements canprovide information directly related to the performance of high-kdielectric, such as the presence of fixed charges, mobile charges orsurface state charges in the high-k or at the high-kdielectric/semiconductor interface.

FIG. 3 illustrates an exemplary flowchart for screening wet processchemicals, such as photoresist strip chemicals, according to someembodiments of the present invention. During the fabrication of an MOScapacitor structure, representing a gate stack of a transistor device,the structure is exposed to a photoresist strip chemical, to simulatethe actual device fabrication of photoresist stripping on gate stackformation. The electrical performance of the MOS capacitor device canindicate the possible side effects of the photoresist strip chemical,permitting a quick ranking of various photoresist strip chemicals. Poorperformance photoresist strip chemicals can be identified and removedwithout the needs to fabricate and test fully-operation devices.

In operation 30, a semiconductor substrate is provided. Thesemiconductor substrate can be a silicon-containing substrate, agermanium-containing substrate, an III-V or II-VI substrate, or anyother substrate containing a semiconductor element. In operation 31, MOScapacitor structures are fabricated, comprising forming a dielectriclayer on the semiconductor substrate and an electrode layer on thedielectric layer. The dielectric layer, preferably comprising a high-kdielectric material, is deposited on the whole substrate. The electrodelayer preferably comprising a refractive metal, and more preferably anitride of a refractive metal, is deposited by a shadow mask process. Atypical shadow mask process comprises disposing an external mask layerhaving a plurality of apertures on the substrate and subjecting thesubstrate with the mask layer to a deposition process, such as physicalvapor deposition (PVD). The deposition material is deposited on thesubstrate through the apertures, forming the electrode pattern.

In operation 32, the substrate is exposed to a wet processing chemical,such as a photoresist strip chemical. For example, the substrate can besubmerged in a liquid bath containing the photoresist strip chemical.Alternatively, the photoresist strip chemical can be disposed on thesubstrate for a certain time before being removed. The exposure can beperformed during any step of the MOS capacitor formation, such as afterforming the dielectric layer, after forming the electrode layer, oroptionally after any additional process, such as an electrode annealprocess or a photoresist coating process. Optional processing steps canbe added, such as a cleaning step or a rinsing step, to simulate theactual transistor fabrication processes.

In operation 33, the capacitor device, comprising an electrode disposedon a dielectric layer on the semiconductor substrate, is electricallytested. The electrical tests can comprise a flatband voltagemeasurement, for example, to determine the presence of charges in thedielectric and at the dielectric/semiconductor interface. The electricaltests can comprise I-V and C-V measurements, including single curve orcycling testing, with varying sweep voltage range, sweep speed, or sweepfrequency, which can offer possible correlation to the defect states.

In some embodiments, control capacitor devices are also fabricated andtested. The control devices are fabricated in the same process steps asthe test devices, except without the photoresist strip exposure step.Comparing the test devices and the control devices can enable theobservation of the performance difference with and without photoresistexposure.

In operation 34, data related to the performance of the capacitor deviceis extracted from the electrical test. In operation 35, photoresiststrip chemicals and process conditions are selected based on acomparison of the device performance.

In some embodiments, the electrical testing of MOS device with exposureto various photoresist strip chemicals can offer a list of processcompatibility between multiple photoresist strip chemicals and othermaterials and conditions of the devices, such as the high-k material orthe metal gate material. This list can enable the optimum devicefabrication process, at least with respect to the selection ofphotoresist strip chemicals.

In some embodiments, the present invention discloses multiple variationsof the exposure of the capacitor device to the photoresist stripchemical. The photoresist strip chemical exposure can occur after theformation of high-k gate dielectric layer, simulating a processcondition of p-type devices during the fabrication of n-type devices.The photoresist strip chemical exposure can occur after the formation ofmetal gate electrode dielectric layer, simulating a fabrication processcondition of transistor devices. The photoresist strip chemical exposurecan occur after coating a layer of photoresist, simulating a photoresiststrip sequence of transistor devices.

FIGS. 4A-4E illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer tophotoresist strip chemical according to some embodiments of the presentinvention. The dielectric layer preferably comprises a high-k dielectricmaterial, and the electrode layer preferably comprises a refractivemetal or a nitride of a refractive metal. In FIG. 4A, a substrate 40 isprovided. In FIG. 4B, a dielectric layer 41 is formed on the substrate40, for example, by chemical vapor deposition (CVD), or by atomic layerdeposition (ALD). Various dielectric materials can be used, for example,high-k dielectric materials or composite layer of silicon dioxide andhigh-k material.

In FIG. 4C, the substrate 40 having the dielectric layer 41 disposedthereon is exposed to a photoresist strip chemical 42. Optionalcleaning, rinsing and drying steps can be included. In FIG. 4D,electrode 43 is formed on the dielectric layer 41. In FIG. 4E, the MOScapacitor device, comprising top electrode 43, dielectric layer 41, andbottom electrode semiconductor substrate 40, is electrically tested, forexample, by probing the top electrode 43.

FIG. 5 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer according to someembodiments of the present invention. The dielectric layer preferablycomprises a high-k dielectric material, and the electrode layerpreferably comprises a refractive metal or a nitride of a refractivemetal. In operation 50, a semiconductor substrate is provided. Inoperation 51, a high-k dielectric layer is formed on the semiconductorsubstrate. In operation 52, the substrate comprising the dielectriclayer is exposed to a photoresist strip chemical. Optional processingsteps can be added, such as a cleaning step or a rinsing step, forexample, to remove the photoresist strip chemical from the substratesurface.

In operation 53, an electrode layer is formed on the dielectric layer onthe semiconductor substrate. Optional processing steps can be added,such as an annealing step, for example, a post metallization anneal withforming gas. In operation 56, the capacitor devices, which comprise anelectrode on a dielectric layer on the substrate, are electricallytested. In some embodiments, control capacitor devices are alsofabricated and tested.

In operation 57, data related to the performance of the capacitor deviceis extracted from the electrical test. In operation 58, photoresiststrip chemicals and process conditions are selected based on acomparison of the device performance.

FIGS. 6A-6E illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer and theelectrode to photoresist strip chemical according to some embodiments ofthe present invention. The dielectric layer preferably comprises ahigh-k dielectric material, and the electrode layer preferably comprisesa refractive metal or a nitride of a refractive metal. In FIG. 6A, asubstrate 60 is provided. In FIG. 6B, a dielectric layer 61 is formed onthe substrate 60. In FIG. 6C, electrode 63 is formed on the dielectriclayer 61.

In FIG. 6D, the substrate 60 having the electrode layer 63 disposed onthe dielectric layer 61 is exposed to a photoresist strip chemical 62.Optional cleaning, rinsing and drying steps can be included. In FIG. 6E,the MOS capacitor device, comprising top electrode 63, dielectric layer61, and bottom electrode semiconductor substrate 60, is electricallytested, for example, by probing the top electrode 63.

FIG. 7 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer and the electrodelayer according to some embodiments of the present invention. Thedielectric layer preferably comprises a high-k dielectric material, andthe electrode layer preferably comprises a refractive metal or a nitrideof a refractive metal. In operation 70, a semiconductor substrate isprovided. In operation 71, a high-k dielectric layer is formed on thesemiconductor substrate. In operation 73, an electrode layer is formedon the dielectric layer on the semiconductor substrate. Optionalprocessing steps can be added, such as a post metallization anneal withforming gas. In operation 75, the substrate comprising the dielectriclayer and the electrode layer is exposed to a photoresist stripchemical. Optional processing steps can be added, such as a cleaningstep or a rinsing step, for example, to remove the photoresist stripchemical from the substrate surface.

In operation 76, the capacitor devices, which comprise an electrode on adielectric layer on the substrate, are electrically tested. In someembodiments, control capacitor devices are also fabricated and tested.In operation 77, data related to the performance of the capacitor deviceis extracted from the electrical test. In operation 78, photoresiststrip chemicals and process conditions are selected based on acomparison of the device performance.

FIGS. 8A-8F illustrate an exemplary process sequence of evaluatingdevice characteristics after exposing the dielectric layer and theelectrode to photoresist strip chemical according to some embodiments ofthe present invention. The dielectric layer preferably comprises ahigh-k dielectric material, and the electrode layer preferably comprisesa refractive metal or a nitride of a refractive metal. In FIG. 8A, asubstrate 80 is provided. In FIG. 8B, a dielectric layer 81 is formed onthe substrate 80. In FIG. 8C, electrode 83 is formed on the dielectriclayer 81. In FIG. 8D, photoresist layer 85 is formed on electrode 83.Alternatively, the photoresist layer 85 can cover the whole substrate(not shown), instead of forming only on the electrode 83.

In FIG. 8E, the substrate 80 having the photoresist layer 85 disposed onthe electrode layer 83 disposed on the dielectric layer 61 is exposed toa photoresist strip chemical 82, which removes the photoresist layer 85.Optional cleaning, rinsing and drying steps can be included. In FIG. 8F,the MOS capacitor device, comprising top electrode 83, dielectric layer81, and bottom electrode semiconductor substrate 80, is electricallytested, for example, by probing the top electrode 83.

FIG. 9 illustrates an exemplary flowchart for screening photoresiststrip chemicals after exposing the dielectric layer and the electrodelayer according to some embodiments of the present invention. Thedielectric layer preferably comprises a high-k dielectric material, andthe electrode layer preferably comprises a refractive metal or a nitrideof a refractive metal. In operation 90, a semiconductor substrate isprovided. In operation 91, a high-k dielectric layer is formed on thesemiconductor substrate. In operation 93, an electrode layer is formedon the dielectric layer on the semiconductor substrate. Optionalprocessing steps can be added, such as a post metallization anneal withforming gas. In operation 94, a photoresist layer is formed on theelectrode layer. The photoresist layer can be a blanket layer, or can beformed only on the electrodes. In operation 95, the substrate comprisingthe dielectric layer and the electrode layer is exposed to a photoresiststrip chemical. Optional processing steps can be added, such as acleaning step or a rinsing step, for example, to remove the photoresiststrip chemical from the substrate surface.

In operation 96, the capacitor devices, which comprise an electrode on adielectric layer on the substrate, are electrically tested. In someembodiments, control capacitor devices are also fabricated and tested.In operation 97, data related to the performance of the capacitor deviceis extracted from the electrical test. In operation 98, photoresiststrip chemicals and process conditions are selected based on acomparison of the device performance.

In some embodiments, other test devices can be fabricated, such asisolated capacitor structure 300 or transistor structure 310. FIGS.10A-10B illustrate other exemplary test structures according to someembodiments of the present invention. FIG. 10A shows an isolatedcapacitor structure 300, comprising top electrode 303 on dielectric 302on substrate 304. The capacitor structure 300 is isolated, for example,from nearby capacitor structures, through isolation regions 301.Electrical testing of isolated capacitor device 300 can be similar toMOS capacitor devices described above.

FIG. 10B shows a transistor structure 310, comprising source/drain 306,gate dielectric 308, gate electrode 309, and spacers 307. Electricaltesting of the transistor device 310 can include transistor data, forexample, threshold voltage or transistor reliability.

In some embodiments, the present invention discloses combinatorialworkflow for evaluating wet processing chemicals, such as photoresiststrip chemicals, to provide optimized process conditions for gate stackformation, preferably for metal gate stack using high-k dielectrics.High productivity combinatorial processing can be a fast and economicaltechnique for electrically screening photoresist chemicals to determinetheir possible side effects on the transistor performance, avoidingpotentially costly device process development through proper selectionof photoresist strip chemicals.

In some embodiments, the dielectric layer is formed through a depositionprocess, such as chemical vapor deposition (CVD), atomic layerdeposition (ALD), or physical vapor deposition (PVD). The electrodelayer can be formed by PVD through a shadow mask. The photoresistexposure can be performed by wet exposure the portions of the substrate.

FIG. 11 illustrates a schematic diagram of a combinatorial PVD systemaccording to an embodiment described herein. Details of thecombinatorial PVD system are described in U.S. patent application Ser.No. 12/027,980 filed on Feb. 7, 2008 and claiming priority to Sep. 5,2007 and U.S. patent application Ser. No. 12/028,643 filed on Feb. 8,2008 and claiming priority to Sep. 5, 2007. Substrate, 1100, is held onsubstrate support, 1102. Substrate support, 1102, has two axes ofrotation, 1104 and 1106. The two axes of rotation are not aligned. Thisfeature allows different regions of the substrate to be accessed forprocessing. The substrate support may be moved in a vertical directionto alter the spacing between the PVD targets and the substrate. Thecombinatorial PVD system comprises multiple PVD assemblies configuredwithin a PVD chamber (not shown). In FIG. 11, three PVD assemblies areshown, 1108 a-1108 c. Those skilled in the art will appreciate that anynumber of PVD assemblies may be used, limited only by the size of thechamber and the size of the PVD assemblies. Typically, four PVDassemblies are contained within the chamber. Advantageously, themultiple PVD assemblies contain different target materials to allow awide range of material and alloys compositions to be investigated.Additionally, the combinatorial PVD system will typically include thecapability for reactive sputtering in reactive gases such as O₂, NH₃,N₂, etc. The PVD assemblies may be moved in a vertical direction toalter the spacing between the PVD targets and the substrate and may betilted to alter the angle of incidence of the sputtered materialarriving at the substrate surface. The combinatorial PVD system furthercomprises a process kit shield assembly, 1110. The process kit shieldassembly includes an aperture, 1112, used to define isolated regions onthe surface. The portion of the process kit shield assembly thatincludes the aperture may have both rotational and translationalcapabilities. The combination of the substrate support movement, PVDassembly movement, and process kit shield assembly aperture movementallows multiple regions of the substrate to be processed in a siteisolated manner wherein each site can be processed without interferencefrom adjacent regions. Advantageously, the process parameters among themultiple site isolated regions can be varied in a combinatorial manner.

FIG. 12 illustrates a schematic diagram of a substrate that has beenprocessed in a combinatorial manner. A substrate, 1200, is shown withnine site isolated regions, 1202 a-1202 i, illustrated thereon. Althoughthe substrate 1200 is illustrated as being a generally square shape,those skilled in the art will understand that the substrate may be anyuseful shape such as round, rectangular, etc. The lower portion of FIG.12 illustrates a top down view while the upper portion of FIG. 12illustrates a cross-sectional view taken through the three site isolatedregions, 1202 g-1202 i. The shading of the nine site isolated regionsillustrates that the process parameters used to process these regionshave been varied in a combinatorial manner. The substrate may then beprocessed through a next step that may be conventional or may also be acombinatorial step as discussed earlier with respect to FIG. 2.

FIG. 13 illustrates a schematic diagram of a combinatorial wetprocessing system according to an embodiment described herein. In thesame manner that the combinatorial PVD system may be used to investigatematerials deposited by PVD, a combinatorial wet system may be used toinvestigate materials deposited by solution-based techniques. An exampleof a combinatorial wet system is described in U.S. Pat. No. 7,544,574cited earlier. Those skilled in the art will realize that this is onlyone possible configuration of a combinatorial wet system. FIG. 13illustrates a cross-sectional view of substrate, 1200, taken through thethree site isolated regions, 1202 g-1202 i similar to the upper portionof FIG. 12. Solution dispensing nozzles, 1300 a-1300 c, supply differentsolution chemistries, 1306 a-1306 c, to chemical processing cells, 1302a-1302 c. FIG. 13 illustrates the deposition of a layer, 1304 a-1304 c,on respective site isolated regions. Although FIG. 13 illustrates adeposition step, other solution-based processes such as cleaning,etching, surface treatment, surface functionalization, etc. may beinvestigated in a combinatorial manner. Advantageously, thesolution-based treatment can be customized for each of the site isolatedregions.

In a typical device fabrication process, different device portions canbe exposed to photoresist strip chemicals, and therefore, in someembodiments, the present invention discloses combinatorially fabricatingand evaluating the effects of photoresist strip chemicals based onvarious process steps in the device fabrication flow.

For example, during a device fabrication process, a photoresist isdeposited on a metal gate stack comprising a metal gate electrodedisposed on a high-k gate dielectric layer disposed on a semiconductorsubstrate. After patterning the metal gate stack, the photoresist layeris exposed to a photoresist strip chemical to completely remove thephotoresist layer before a subsequent process step. In some embodiments,the present invention discloses methods to evaluate the side effects ofthe photoresist strip chemical under similar configuration. As anexample, a photoresist layer is deposited on a metal gate stackcomprising a metal electrode on a high-k dielectric layer on asubstrate. The metal gate stack forms a MOS capacitor structure that canenable electrical testing to assess the integrity of the dielectriclayer and the dielectric-semiconductor interface. The substrate with themetal gate stack is then exposed to a photoresist strip chemical, andelectrical tests are performed on the MOS capacitor structure.

As another example, during the fabrication of n-type (or p-type) device,the high-k dielectric area of the p-type (or n-type, respectively)device is protected from being processed, for example, by a photoresistmasking. Thus the high-k gate dielectric layer of the p-type device isexposed to photoresist strip chemical during the photoresist strippingprocess of the n-type device. In some embodiments, the present inventiondiscloses methods to evaluating the side effects of the photoresiststrip chemical under similar configuration. As an example, a photoresistlayer is deposited on a high-k dielectric layer on a substrate. Thesubstrate with the high-k dielectric layer is then exposed to aphotoresist strip chemical. Afterward, metal electrode is deposited onthe high-k dielectric layer to form MOS capacitor device that can enableelectrical testing to assess the integrity of the dielectric layer andthe dielectric-semiconductor interface.

In some embodiments, the present invention discloses testing structuresfor combinatorially evaluating the effects of photoresist stripchemicals. The photoresist layer can be omitted from the test structuresto simplify the process flow. Further, accelerated testing can beperformed to evaluate the process window of the photoresist stripexposure. For example, the exposure can be longer or at highertemperature than normal fabrication processes.

For example, the high-k dielectric layer can be exposed to a photoresiststrip chemical without a photoresist layer in the test structures. Atest structure can comprise a high-k dielectric layer deposited on asubstrate. The substrate with the high-k dielectric layer is thenexposed to a photoresist strip chemical. Metal electrode is thendeposited on the high-k dielectric layer to form MOS capacitor devicethat can enable electrical testing. Optional processes can be added,such as cleaning and rinsing to remove any residue of the photoresiststrip chemical. Post metallization anneal can be performed for the metalelectrodes.

Alternatively, a high-k dielectric layer and a metal electrode can beexposed to a photoresist strip chemical without a photoresist layer inthe test structures. A test structure can comprise a metal electrodelayer deposited a high-k dielectric layer which is deposited on asubstrate. The substrate with the metal electrode/high-k dielectriclayer is then exposed to a photoresist strip chemical. The metalelectrode and the high-k dielectric layer can form a MOS capacitordevice that can enable electrical testing. Other test structures canalso be used.

The following description describes exemplary processes using teststructures. Other test or actual structures can also be used. Acombinatorial testing process is described involving exposing only thedielectric layer to wet chemicals before electrically testing the MOSdevices. In some embodiments, photoresist strip chemicals are screenedfor optimizing a metal gate stack formation using a high-k gatedielectric material. The photoresist strip chemicals screening processcomprises forming a dielectric layer on a semiconductor substrate,combinatorially processing multiple regions of the semiconductorsubstrate comprising exposing the dielectric layer in a region of themultiple regions to a photoresist strip chemical, wherein thephotoresist strip chemical is varied across the multiple regions of thesemiconductor substrate, then forming a plurality of electrodes on thedielectric layer, each of the multiple regions having at least anelectrode, and then electrical testing a plurality of capacitor devices,each capacitor device comprising the dielectric layer sandwiched betweenan electrode and the semiconductor substrate. The various electricaltesting data are compared to obtain a photoresist strip chemical amongthe plurality of photoresist strip chemicals meeting a desiredrequirement. The dielectric layer preferably comprises a high-kmaterial, such as hafnium oxide, hafnium silicon oxide, zirconium oxide,zirconium silicon oxide, or aluminum oxide. Other high-k materials canalso be used.

In some embodiments, a control capacitor device is formed in a controlregion on the semiconductor substrate. The control capacitor possessessimilar structure and fabrication process as the test capacitor devices,but without the photoresist strip exposure. For example, the controlcapacitor device can comprise a dielectric layer sandwiched between anelectrode and the semiconductor substrate, wherein the control region,e.g., the portion encompassing the substrate, the dielectric layer, andthe electrode layer, is not exposed to photoresist strip chemicals. Thecontrol capacitor device is electrical tested, and the electricaltesting data of the control device is compared with those of a testdevice having the dielectric layer exposed to a photoresist stripchemical.

In some embodiments, the electrical testing comprises at least one of anI-V measurement, a C-V measurement, a flatband voltage shiftmeasurement, or an effective work function measurement.

In some embodiments, additional process steps can be added, such ascleaning, rinsing after the photoresist strip chemical exposure, or apost metallization anneal for the metal electrodes.

In some embodiments, the electrode layer can comprise a metal materialor a metal alloy material, such as titanium, tantalum, or ruthenium. Theelectrode layer also can comprise a nitride metal material or nitridealloy material, such as titanium nitride, tantalum nitride, rutheniumnitride, titanium aluminum nitride, or titanium lanthanum nitride. Theelectrodes are preferably formed by a shadow mask deposition process. Ina shadow mask deposition process, a thin mask, for example, made ofstainless steel material, having a plurality of aperture openingstherethrough, is disposed in intimate contact with a substrate beforesubjecting the substrate to a metal deposition, such as a PVD process.

Another combinatorial testing process is described involving exposingboth the dielectric layer and the electrode to wet process chemicalsbefore electrically testing the MOS devices. In some embodiments,photoresist strip chemicals are screened for optimizing a metal gatestack formation using a high-k gate dielectric material. The photoresiststrip chemicals screening process comprises forming a dielectric layeron a semiconductor substrate, forming a plurality of electrodes on thedielectric layer, and then combinatorially processing multiple regionsof the semiconductor substrate. Each of the multiple regions preferablycomprises at least an electrode, e.g., at least a MOS capacitor device.The combinatorially processing comprises exposing the electrode and thedielectric layer in a region of the multiple regions to a photoresiststrip chemical, with the photoresist strip chemicals varied in acombinatorial manner across the multiple regions of the semiconductorsubstrate. Afterward, the plurality of capacitor devices is electricallytested, with each capacitor device comprising the dielectric layersandwiched between an electrode and the semiconductor substrate. Thevarious electrical testing data are compared to obtain a photoresiststrip chemical among the plurality of photoresist strip chemicalsmeeting a desired requirement. The dielectric layer preferably comprisesa high-k material.

In some embodiments, a control capacitor device is formed in a controlregion on the semiconductor substrate. The control capacitor device iselectrical tested, and the electrical testing data of the control deviceis compared with those of a test device having the dielectric layerexposed to a photoresist strip chemical.

FIG. 14 illustrates a flow diagram for forming simple test structuresaccording to an embodiment described herein. As discussed in relation toFIG. 3, several of the layers or process steps provide opportunities toapply combinatorial techniques to the development and investigation ofthe materials and treatments for the layers. For evaluating photoresiststrip chemicals, parameter candidates include the high-k dielectriclayer, the photoresist strip exposure, and the metal electrode layer. Asmentioned previously, examples of suitable high-k dielectric layerscomprise hafnium oxide, zirconium oxide, aluminum oxide, or any mixturecombination, etc. hafnium oxide and hafnium silicon oxide are thematerial most often used currently as the high-k dielectric layer formetal gate stack devices. The high-k dielectric layer may be depositedusing chemical vapor deposition (CVD), atomic layer deposition (ALD), orplasma enhanced CVD or ALD. The effects of photoresist strip chemicalson the high-k layer and the high-k/semiconductor interface may beinvestigated using HPC techniques by varying process parameters such ashigh-k material, deposition process condition, surface preparationprocess, interface layer (such as a silicon oxide layer), etc. These aremeant to be illustrative parameters and those skilled in the art will beable to apply HPC techniques to any of the commonly used processparameters.

A process step that may be investigated using HPC techniques includesthe photoresist strip exposure. The photoresist strip exposure isdesigned to strip the photoresist layer after patterning the metal gatestack. The photoresist strip exposure may be investigated using HPCtechniques by varying process parameters such as strip chemicals,chemical concentration, exposure time, chemical temperature, chemicalstirring rate, etc. For example, photoresist strip chemicals can beselected from a list of commercially available chemicals, in addition tospecially designed chemicals. These are meant to be illustrativeparameters and those skilled in the art will be able to apply HPCtechniques to any of the commonly used process parameters.

Another layer that may be investigated using HPC techniques includes themetal gate electrode layer. Examples of suitable metal gate electrodematerials comprise titanium, tantalum, aluminum, lanthanum, theiralloys, nitrides and nitride alloys, etc. Typically, PVD is thepreferred method of deposition for the metal gate electrode layer. Thedeposition of the metal electrode layer by PVD may be investigated usingHPC techniques by varying process parameters such as material, power,pressure, target to substrate distance, atomic ratio, etc. These aremeant to be illustrative parameters and those skilled in the art will beable to apply HPC techniques to any of the commonly used processparameters.

Returning to FIG. 14, through the use of a combination of conventionaland combinatorial processing systems (i.e. systems capable of processingmultiple isolated regions on a single substrate) a number oftrajectories through the various systems illustrated in the flow diagramof FIG. 14 can be envisioned. In FIG. 14, the high-k dielectric layermay be deposited in a conventional processing manner, 1400, in someembodiments where the high-k dielectric layer is not a variable. Asdiscussed previously, the photoresist strip exposure may be processed ina conventional processing manner, 1404, or in a site isolatedcombinatorial processing manner, 1412. The metal electrode layer may bedeposited in a conventional processing manner, 1406, in some embodimentswhere the metal electrode is not a variable. The anneal process, such asa post metallization anneal in forming gas, may be processed in aconventional processing manner, 1408. After the deposition of thevarious layers and subsequent processing, the various MOS capacitordevices represented by each of the site isolated regions may be testingin step 1416, and the results evaluated in step, 1418. As discussedpreviously, the results will form the basis for additional cycles ofinvestigation through HPC techniques to identify materials and processconditions that evaluate the suitability of photoresist strip exposurein devices having the given high-k dielectric and metal gate electrode.

Using the simple diagram in FIG. 14, there are two possible trajectoriesthrough the process sequence, which encompass all of the possiblecombinations of conventional and combinatorial processing illustrated.Those skilled in the art will understand that HPC techniques may beapplied to other processes not illustrated such as anneal treatments,cleaning, etching, rinsing, surface treatments, surfacefunctionalization, etc. As more variable process steps are included, thetotal number of required experiments increases dramatically. Thisillustrates the benefits of using HPC techniques to limit the number ofsubstrates to a manageable number and minimize the cost of thedevelopment program.

The illustrated simple diagram represents a possible evaluation processfor the side effects of various photoresist strip chemicals on aspecific high-k gate dielectric and metal gate electrode. The variablesfurther include other process windows, such as the exposure temperature,time, and concentration.

FIG. 15 illustrates a flow diagram for forming another exemplary teststructure evaluation according to an embodiment described herein.Additional layers can be included in the test methodology, including themetal gate electrode layer. Through the use of a combination ofconventional and combinatorial processing systems (i.e. systems capableof processing multiple isolated regions on a single substrate) a numberof trajectories through the various systems illustrated in the flowdiagram of FIG. 15 can be envisioned. In FIG. 15, the high-k dielectriclayer may be deposited in a conventional processing manner, 1500, insome embodiments where the high-k dielectric layer is not a variable. Asdiscussed previously, the photoresist strip exposure may be processed ina conventional processing manner, 1504, or in a site isolatedcombinatorial processing manner, 1512. The metal electrode layer may bedeposited in a conventional processing manner, 1506, or in a siteisolated combinatorial processing manner, 1514. The anneal process, suchas a post metallization anneal in forming gas, may be processed in aconventional processing manner, 1508. After the deposition of thevarious layers and subsequent processing, the various MOS capacitordevices represented by each of the site isolated regions may be testingin step 1516, and the results evaluated in step, 1518. As discussedpreviously, the results will form the basis for additional cycles ofinvestigation through HPC techniques to identify materials and processconditions that evaluate the suitability of photoresist strip exposurewith respect to different metal gate electrode in devices having thegiven high-k dielectric.

Using the simple diagram in FIG. 15, there are four possibletrajectories through the process sequence. These four trajectoriesencompass all of the possible combinations of conventional andcombinatorial processing illustrated. Those skilled in the art willunderstand that HPC techniques may be applied to other processes notillustrated such as anneal treatments, cleaning, rinsing, etching,surface treatments, surface functionalization, etc. As more variableprocess steps are included, the total number of required experimentsincreases dramatically. This illustrates the benefits of using HPCtechniques to limit the number of substrates to a manageable number andminimize the cost of the development program.

FIG. 16 illustrates a flow diagram for forming another exemplary teststructure evaluation according to an embodiment described herein.Additional layers can be included in the test methodology, including themetal gate electrode layer and the high-k dielectric. Through the use ofa combination of conventional and combinatorial processing systems (i.e.systems capable of processing multiple isolated regions on a singlesubstrate) a number of trajectories through the various systemsillustrated in the flow diagram of FIG. 16 can be envisioned. In FIG.16, the high-k dielectric layer may be deposited in a conventionalprocessing manner, 1600, or in a site isolated combinatorial processingmanner, 1610. As discussed previously, the photoresist strip exposuremay be processed in a conventional processing manner, 1604, or in a siteisolated combinatorial processing manner, 1612. The metal electrodelayer may be deposited in a conventional processing manner, 1606, or ina site isolated combinatorial processing manner, 1614. The annealprocess, such as a post metallization anneal in forming gas, may beprocessed in a conventional processing manner, 1608. After thedeposition of the various layers and subsequent processing, the variousMOS capacitor devices represented by each of the site isolated regionsmay be testing in step 1616, and the results evaluated in step, 1618. Asdiscussed previously, the results will form the basis for additionalcycles of investigation through HPC techniques to identify materials andprocess conditions that evaluate the suitability of photoresist stripexposure with respect to different metal gate electrode and high-kdielectric.

Using the simple diagram in FIG. 16, there are eight possibletrajectories through the process sequence. These eight trajectoriesencompass all of the possible combinations of conventional andcombinatorial processing illustrated. Those skilled in the art willunderstand that HPC techniques may be applied to other processes notillustrated such as anneal treatments, cleaning, rinsing, etching,surface treatments, surface functionalization, etc. As more variableprocess steps are included, the total number of required experimentsincreases dramatically. This illustrates the benefits of using HPCtechniques to limit the number of substrates to a manageable number andminimize the cost of the development program.

FIG. 17 illustrates another flow diagram for forming an exemplary teststructure evaluation according to an embodiment described herein.Several of the layers provide opportunities to apply combinatorialtechniques to the development and investigation of the photoresist stripchemicals. Layer candidates include the high-k dielectric layer, themetal electrode layer, and the photoresist layer. These three layers canbe processed in a conventional processing manner, or in a site isolatedcombinatorial processing manner. Sandwiched between these layers are thephotoresist strip exposure, which can be skipped (no operation), orprocessed in a site isolated combinatorial processing manner.

Through the use of a combination of conventional and combinatorialprocessing systems, a number of trajectories through the various systemsillustrated in the flow diagram of FIG. 17 can be envisioned. In FIG.17, the high-k dielectric layer may be deposited in a conventionalprocessing manner, 1710, or in a site isolated combinatorial processingmanner, 1720. The photoresist strip exposure may be skipped, 1701, orprocessed in a site isolated combinatorial processing manner, 1721. Themetal electrode layer may be deposited in a conventional processingmanner, 1712, or in a site isolated combinatorial processing manner,1722. The photoresist strip exposure may be skipped, 1703, or processedin a site isolated combinatorial processing manner, 1723. Thephotoresist layer may be skipped, 1704, deposited in a conventionalprocessing manner, 1714, or in a site isolated combinatorial processingmanner, 1724. The photoresist strip exposure may be skipped, 1705, orprocessed in a site isolated combinatorial processing manner, 1725.

After the deposition of the various layers and subsequent processing,the various MOS capacitor devices represented by each of the siteisolated regions may be testing in step 1730, and the results evaluatedin step, 1731. As discussed previously, the results will form the basisfor additional cycles of investigation through HPC techniques toidentify materials and process conditions that evaluate the suitabilityof photoresist strip exposure with respect to different metal gateelectrode and high-k dielectric. Control devices can be included in theprocess sequence, for example, through the sequence 1710/1720 to 1701 to1712/1722 to 1703 to 1704 to 1705.

FIG. 18 illustrates a flatband voltage shift comparison between 8different photoresist strip chemicals according to some embodiments ofthe present invention. The electrical data is collected from processsequence 1710-1721-1712-1703-1704-1705, together with additional stepsof water rinsing after photoresist strip exposure, and a postmetallization anneal after the electrode deposition. As shown,photoresist strip chemicals can have different side effects on thedevice characteristics, represented by the flatband voltage shift, whichis an indication of the fixed or mobile charges generated in the high-kdielectric or at the high-k dielectric-semiconductor interface.Photoresist strip chemical #2 is best, followed closely by photoresiststrip chemical #3, while photoresist strip chemical #7 is acceptable.Other photoresist chemicals are below an acceptable criterion, which isroughly about 10 mV for a first screening test.

Additional electrical data can be collected, such as I-V and C-V curves.For example, electrical data measurements include cycling I-V curvesmeasuring I-V hysteresis and with changing I-V sweep speed, and cyclingC-V curves measuring C-V hysteresis and with changing C-V sweep speedand frequency. The I-V and C-V data can disclose possible correlation ofthe photoresist strip chemical exposure to defect states.

Although the foregoing examples have been described in some detail forpurposes of clarity of understanding, the invention is not limited tothe details provided. There are many alternative ways of implementingthe invention. The disclosed examples are illustrative and notrestrictive.

What is claimed is:
 1. A method for screening photoresist stripchemicals in a combinatorial manner comprising forming a dielectriclayer on a semiconductor substrate; defining a plurality of siteisolated regions on the dielectric layer; forming an electrode in eachsite isolated region, wherein the electrode, dielectric layer, andsubstrate form a capacitor device; applying a photoresist strip chemicalto each site isolated region, wherein at least one of the composition orthe application condition of the photoresist strip chemical is varied ina combinatorial manner between the site isolated regions; and measuringan electrical characteristic of the capacitor device formed within eachsite isolated region.
 2. The method of claim 1 further comprisingcomparing the electrical characteristic of the capacitor device in onesite isolated region with the electrical characteristic of the capacitordevice in another site isolated region.
 3. A method for screeningphotoresist strip chemicals in a combinatorial manner, the methodcomprising forming a dielectric layer on a semiconductor substrate;defining a plurality of site isolated regions on the dielectric layer;applying a photoresist strip chemical to each site isolated region,wherein at least one of the composition or the application condition ofthe photoresist strip chemical is varied in a combinatorial mannerbetween the site isolated regions; and forming an electrode in each siteisolated region, wherein the electrode, dielectric layer, and substrateform a capacitor device; measuring an electrical characteristic of thecapacitor device formed within each site isolated region.
 4. The methodof claim 3 further comprising comparing the electrical characteristic ofthe capacitor device in one site isolated region with the electricalcharacteristic of the capacitor device in another site isolated region.5. The method of claim 3 wherein a site isolated region of the pluralityof site isolated regions is a control site isolated region, wherein theelectrode, dielectric layer, and substrate in the control site isolatedregion form a control capacitor device, and wherein varying at least oneof the composition or the application condition of the photoresist stripchemical in a combinatorial manner between the site isolated regionscomprises not applying photoresist strip chemicals to the control siteisolated region, the method further comprising measuring an electricalcharacteristic of the control capacitor device; comparing the electricalcharacteristic of the capacitor device with the electricalcharacteristic of the control capacitor device.
 6. The method of claim 3wherein the electrical characteristic measurement comprises at least oneof an I-V measurement, a C-V measurement, a flatband voltage shiftmeasurement, or an effective work function measurement.
 7. The method ofclaim 3 wherein the dielectric layer comprises a high-k dielectricmaterial.
 8. The method of claim 3 wherein the dielectric layercomprises hafnium oxide.
 9. The method of claim 3 wherein the electrodecomprises a metal.
 10. The method of claim 3 wherein the electrodecomprises TiN, TiAlN, or TiLaN.
 11. The method of claim 3 furthercomprising annealing the semiconductor substrate after forming theelectrode.
 12. The method of claim 3 wherein the electrode is formed bya shadow mask deposition process.
 13. The method of claim 3 whereinvarying at least one of the composition or the application condition ofthe photoresist strip chemical in a combinatorial manner between thesite isolated regions comprises not applying photoresist strip chemicalsto a site isolated region.
 14. A method for screening photoresist stripchemicals in a combinatorial manner, the method comprising forming adielectric layer on a semiconductor substrate; forming a plurality ofelectrodes on the dielectric layer; defining a plurality of siteisolated regions on the dielectric layer, wherein each site isolatedregion comprises an electrode of the plurality of electrodes, andwherein the electrode, dielectric layer, and substrate form a capacitordevice; applying a photoresist strip chemical to each site isolatedregion, wherein at least one of the composition or the applicationcondition of the photoresist strip chemical is varied in a combinatorialmanner between the site isolated regions; and measuring an electricalcharacteristic of the capacitor device formed within each site isolatedregion.
 15. The method of claim 14 further comprising comparing theelectrical characteristic of the capacitor device in one site isolatedregion with the electrical characteristic of the capacitor device inanother site isolated region.
 16. The method of claim 14 wherein a siteisolated region of the plurality of site isolated regions is a controlsite isolated region, wherein the electrode, dielectric layer, andsubstrate in the control site isolated region form a control capacitordevice, and wherein varying at least one of the composition or theapplication condition of the photoresist strip chemical in acombinatorial manner between the site isolated regions comprises notapplying photoresist strip chemicals to the control site isolatedregion, the method further comprising measuring an electricalcharacteristic of the control capacitor device; comparing the electricalcharacteristic of the capacitor device with the electricalcharacteristic of the control capacitor device.
 17. The method of claim14 wherein the electrical characteristic measurement comprises at leastone of an I-V measurement, a C-V measurement, a flatband voltage shiftmeasurement, or an effective work function measurement.
 18. The methodof claim 14 wherein the dielectric layer comprises a high-k dielectricmaterial.
 19. The method of claim 14 wherein the plurality of electrodescomprise a metal.
 20. The method of claim 14 wherein varying at leastone of the composition or the application condition of the photoresiststrip chemical in a combinatorial manner between the site isolatedregions comprises not applying photoresist strip chemicals to a siteisolated region.